Composition for coating shaped articles or elastomeric materials

ABSTRACT

The invention relates to a composition, to a process for its preparation and to a method of coating shaped articles or elastomeric materials, where the composition can be prepared using 
     (1) polymer components selected from the group consisting of 
     (A1) polyorganosiloxanes comprising units (T units) of the formula (R 1 Si—O 3/2 ) and optionally, units (M units) of the formula (R 3 Si—O 1/2 ) 
     (A2) polyorganosiloxanes comprising units (Q units) of the formula (Si—O 4/2 ) and, optionally, units (M units) of the formula (R 3 Si—O 1/2 ) 
      in which 
     R is identical or different and represents unhalogenated or halogenated hydrocarbon radicals having 1 to 18 carbon atom(s) per radical or OR 1 , where 
     R 1  is identical or different and represents hydrogen or a monovalent, unsubstituted or substituted hydrocarbon radical having 1 to 8 carbon atom(s), 
      with the proviso that there are from 0.01% to 3.0% by weight, preferably from 0.01% to 1% by weight, of Si-bonded radicals OR 1    
     (B) vinyl chloride-hydroxypropyl acrylate copolymers, 
     (C) vinyl acetate-ethylene copolymer, 
     (D) polyvinyl chloride, 
     (E) polyamide, 
     (F) polyester, 
     (G) acrylate-polyester copolymers, 
     (H) polyamide-polyester copolymers, 
     (I) vinyl acetate-polyester copolymers, and 
     (J) Monomeric (meth)acrylates, with the proviso that they are copolymerized with Si-bonded (meth)acrylate group-containing silanes, 
     (2) a silane of the formula R 3   x Si(OR 2 ) 4-x , where 
     R 2  is a monovalent, unsubstituted or substituted hydrocarbon radical, 
     R 3  is a monovalent organic radical, 
     x represents 0 or 1, 
     (3) optionally, a solvent, 
     (4) optionally, a catalyst and 
     (5) optionally, water.

This is a division of application Ser. No. 08/568,071, filed Dec. 6,1995, now U.S. Pat. No. 6,107,418.

BACKGROUND OF INVENTION

The present invention relates to a composition to a process for itspreparation and to a method of coating shaped articles or elastomericmaterials.

FIELD OF INVENTION

It is known that silicone rubber surfaces have high coefficients ofstatic and sliding friction. Silicone rubbers with a Shore A hardness ofbelow 70 in particular exhibit highly blocking properties and are easilysoiled.

AT-250682 describes a process for the coating of a base material, inwhich the base material is coated with an aqueous solution of thehydrolysates of an organosilane which has an acryloxy radical, and iscured. In a second step, the prime surface is coated with apolymerizable resin, especially polyester resin. This process serves toincrease the strength of compression moldings or laminates.

EP 220 804 describes a glass fabric which has a first layer of apolydiorganosiloxane which contains methyl and phenyl groups in a ratioof 0.25 to 3.7, compared with a coating which has only methyl groups,the glass fabric coated with the polydiorganosiloxane being transparentor translucent. A second layer then consists of a polydimethylsiloxane.A third polyorganosiloxane layer is applied to this second layer.

U.S. Pat. No. 4,489,127 describes coatings for fibreglass roofs, whichcomprise diorganosiloxanes which contain dimethylsiloxane units andphenylmethyl units and copolymers of R₃SiO_(1/2) in SiO_(4/2) units.

U.S. Pat. No. 3,639,155 describes dirt-repellent organosiloxane coatingswhich comprise dimethylsiloxane units, phenylmethylsiloxane units andmonomethylsiloxane units, and also organosiloxane units which containSi-bonded acetoxy, alkoxy or ketoxy groups.

A disadvantage of the prior art is that the known coatings, owing to thecontent of phenyl groups, give off aromatic substances when heated or inthe event of fire. Further disadvantages of the prior art are that thecoefficient of friction is unchanged or reduced only insignificantly,and that phenyl radicals on the silicon are difficult to attain.

SUMMARY OF INVENTION

The object of the present invention is to improve the known coatings andto provide coatings having improved dirt-repellent properties and alower coefficient of friction.

The present invention relates to a composition which can be preparedusing

(1) polymer components selected from the group consisting of

(A1) polyorganosiloxanes comprising units (T units) of the formula(R₁Si—O_(3/2)) and optionally, units (M units) of the formula(R₃Si—O_(1/2))

(A2) polyorganosiloxanes comprising units (Q units) of the formula(Si—O_(4/2)) and, optionally, units (M units) of the formula(R₃Si—O_(1/2))

 in which

R is identical or different and represents unhalogenated or halogenatedhydrocarbon radicals having 1 to 18 carbon atom(s) per radical or OR¹,where

R¹ is identical or different and represents hydrogen or a monovalent,unsubstituted or substituted hydrocarbon radical having 1 to 8 carbonatom(s),

 with the proviso that there are from 0.01% to 3.0% by weight,preferably from 0.01% to 1% by weight, of Si-bonded radicals OR¹

(B) vinyl chloride-hydroxypropyl acrylate copolymers,

(C) vinyl acetate-ethylene copolymer,

(D) polyvinyl chloride,

(E) polyamide,

(F) polyester,

(G) acrylate-polyester copolymers,

(H) polyamide-polyester copolymers,

(I) vinyl acetate-polyester copolymers, and

(J) Monomeric (meth)acrylates, with the proviso that they arecopolymerized with Si-bonded (meth)acrylate group-containing silanes,

(2) a silane of the formula R³ _(x)Si(OR²)_(4−x), where

R² is a monovalent, unsubstituted or substituted hydrocarbon radical,

R³ is a monovalent organic radical,

x represents 0 or 1,

(3) optionally, a solvent,

(4) optionally, a catalyst and

(5) optionally, water.

Examples of radicals R are preferably alkyl radicals, such as themethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl,n-pentyl, isopentyl, neopentyl and tert-pentyl radical; hexyl radicals,such as the n-hexyl radical; heptyl radicals, such as the n-heptylradical; octyl radicals, such as the n-octyl radical and iso-octylradicals such as the 2,2,4-trimethylpentyl radical; nonyl radicals, suchas the n-nonyl radical; decyl radicals, such as the n-decyl radical;dodecyl radicals; such as the n-dodecyl radical; octadecyl radicals,such as the n-octadecyl radical; alkenyl radicals, such as the vinyl andthe allyl radicals; cycloalkyl radicals, such as cyclopentyl,cyclohexyl, cycloheptyl radicals and methylcyclohexyl radicals.

Examples of substituted radicals R are cyanoalkyl radicals, such as theβ-cyanoethyl radical, and halogenated hydrocarbon radicals, for examplehaloalkyl radicals, such as the 3,3,3-trifluoro-n-propyl radical, the2,2,2,2′,2′,2′-hexafluoroisopropyl radical, the heptafluoroisopropylradical.

On the grounds of greater ease of accessibility, methyl or ethylradicals are preferred as radical R.

Radical R¹ is preferably hydrogen atom and unsubstituted or substitutedhydrocarbon radicals having 1 to 8 carbon atom(s), in which contexthydrogen and alkyl radicals having 1 to 3 carbon atom(s), especially themethyl, ethyl, and isopropyl radical, are more preferred.

Examples of radicals R¹ are the examples given for the radical R whichhave 1 to 8 carbon atom(s).

Examples of radicals R² are preferably unsubstituted or substitutedhydrocarbon radicals having 1-18 carbon atom(s), more preferably alkylradicals, such as the methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentylradical; hexyl radicals, such as the n-hexyl radical and isohexylradicals; heptyl radicals, such as the n-heptyl radical and isoheptylradical; octyl radicals, such as the n-octyl radical and isooctylradicals, such as the 2,2,4-trimethylpentyl radical. The methyl andethyl radical is preferred. Examples of hydrocarbon radicals R² whichcan be substituted by an ether oxygen atom are the methoxyethyl, theethoxyethyl, the methoxy-n-propyl and the methoxy-isopropyl radical.

Examples of radicals R³ are preferably unsubstituted or substitutedhydrocarbon radicals having 1-18 carbon atom(s), more preferably alkylradicals, such as the methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentylradical; hexyl radicals, such as the n-hexyl radical and isohexylradicals; heptyl radicals, such as the n-heptyl radical-and isoheptylradical; octyl radicals, such as the n-octyl radical and isooctylradicals, such as the 2,2,4-trimethylpentyl radical; nonyl radicals,such as the n-nonyl radical and isononyl radicals; decyl radicals, suchas the n-decyl radical and isodecyl radicals; dodecyl radicals, such asthe n-dodecyl radical and isododecyl radicals; octadecyl radicals, suchas the n-octadecyl radical and isooctadecyl radicals; alkenyl radicals,such as the vinyl and the allyl radicals; cycloalkyl radicals, such ascyclopentyl, cyclohexyl, cycloheptyl radicals, and methylcycloheptylradicals; aryl radicals, such as the phenyl, naphthyl, anthryl andphenanthryl radicals; alkaryl radicals, such as o-, m-, p-tolylradicals, xylyl radicals, ethylphenyl radicals, o-, m-, p-vinylphenylradicals and the nonylphenyl radical; and aralkyl radicals, such as thebenzyl radical, the α- and the β-phenyl ethyl radical; isocyanoalkylradicals such as the isocyanopropyl radical, isocyanoethyl radical,isocyanohexyl radical, isocyanooctyl radical, the isocyanopropyl radicalbeing preferred, and (meth)acryloxy radical such as themethacryloxypropyl radical, acryloxypropyl radical, methacryloxyhexylradical, acryloxyhexyl radical, the methacryloxypropyl radical beingpreferred.

Examples of halogenated hydrocarbon radicals R are haloalkyl radicals,such as the 3-chloro-n-propyl radical, the 3,3,3-trifluoro-n-propylradical, the 2,2,2,2′,2′,2′-hexafluoroisopropyl radical theheptafluoroisopropyl radical, and haloaryl radicals, such as the o-, m-and p-chlorophenyl radical.

In the polyorganosiloxanes (A1) the ratio of M units to T units is from0 to 1.8:1, preferably from 0.1 to 1.2:1 and more preferably 0.3 to0.8:1, and in the polyorganosiloxanes (A2) the ratio of M units to Qunits is from 0.00 to 2.7:1, preferably from 0.01 to 2.1:1 morepreferably 0.1 to 1.8:1.

The polyorganosiloxanes according to the invention form a polymercomprising 2 to 500, preferably 4 to 300 monomer units.

The polymer components (A1) and (A2) can be employed alone or asmixtures or reaction products of the organosiloxane units. Preferredpolymer components are those such as resin solution K or resin solutionK 0118 from Wacker-Chemie GmbH. These resins can preferably be dissolvedin solvents, such as toluene, xylene, acetone, ethyl acetate, ethanol.The solvents are employed in quantities of from 10% to 98% by weight,preferably from 30% to 98% by weight, based on the overall weight of thepolymer components.

The polymer components (A1) and (A2) can be employed alone or asmixtures in a ratio of from 1:20 to 20:1, preferably from 1:10 to 10:1.

In addition to the polymer components (A1) and (A2) it is also possibleto employ as polymer components (B) vinyl chloride-hydroxypropylacrylate copolymers. Such products are offered commercially by VinnolitGmbH under the name Vinnolit E 15/40 A. It is also possible to employ(C) copolymers of vinyl acetate and ethylene as polymer components. Bymeans of the processes known in the literature, copolymers in everydesired ratio can be prepared from both monomers.

As further polymer components it is possible to employ, (D) polyvinylchloride, (E) polyamide, (F) polyester, (G) acrylate-polyestercopolymers, (H) polyamide-polyester copolymers or (I) vinylacetate-polyester copolymers or (J) Monomeric (meth)acrylates, such asmethyl methacrylate, butyl methacrylate, which are polymerized in thereaction mixture. The polymer components (A1), (A2), (B) and (C) arepreferred, the polymer components (A1) and (A2) are more preferred.

The polymer components are present in the compositions according to theinvention in quantities of 2% to 70% by weight. A quantity of 5% to 50%by weight is preferred, a quantity of 10% to 40% by weight is morepreferred.

Preferred examples of silanes (2) are methacryloxypropyltrimethoxysilane(trade name Silan GF 31—Wacker-Chemie GmbH), methyltriethoxysilane(trade name Silan Ml-triethoxy—Wacker-Chemie GmbH), vinyltriethoxysilane(trade name Silan GF 56—Wacker-Chemie GmbH), tetraethoxysilane (tradename TES 28—Wacker-Chemie GmbH), mixtures of low molecular weighthydrolysis products of tetraethoxysilane (trade name TES40—Wacker-Chemie GmbH), methyltrimethoxysilane (trade name M1trimethoxy—Wacker-Chemie GmbH), isocyanatopropyl trimethoxysilane (tradename Silan Y 9030 UCC).

The silanes are present in quantities of 0.1% to 20% by weight,preferably of 0.5% to 10% by weight.

The polymer components are employed with the silanes (2) or mixturesthereof in the ratio of 100:1 to 100:30, more preferably from 100:2 to100:20.

The compositions are preferably prepared in organic solvents, such astetahydrofuran, toluene, acetone, naphtha, benzine, methyl ethyl ketone,xylene, butyl alcohol, ethyl acetate, isopropyl acetate, isopropanol.

Organic solvents are present in quantities of from 10% to 90% by weight,preferred are 30% to 85% by weight.

The compositions are mixed if desired with condensation catalysts, suchas preferably organotin compounds or organozirconium compounds such as,preferably, zirconium butylate, dibutyltin dilaurate, dibutyltin oxide,dioctyltin dilaurate, dibutyltin diacetate.

Preferred among these condensation catalysts are dibutyltin dilaurate,dibutyltin acetate, zirconium butylate.

The condensation catalysts are present in quantitites of between 0% to10% by weight. Preferred quantities are 0% to 5% by weight, morepreferred quantities are 0% to 2% by weight.

A preferred source of free radicals, which are preferably employed inthe polymer component (J), are peroxides, especially organic peroxides.Examples of such organic peroxides are peroxyketal, i.e.,1,1-bis(tertbutylperoxy)-3,3,5-trimethylcyclohexane,2,2-bi(tertbutylperoxy)butane and the like, diacyl peroxides, such asacetyl peroxide, isobutyl peroxide, benzoyl peroxide and the like,dialkyl peroxides, such as di-tert-butyl peroxide, tert-butyl cumylperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(tertbutylperoxy)hexanet-butyl perethylhexanoates and the like and per-esters, such astert-butyl peroxyisopropyl carbonate. Preference is given to t-butylperethylhexanoate (trade name Peroxan PO) Interox TBPIN.

Peroxides are preferably used in quantities of from 0% to 5% by weight,in particular from 0% to 3% by weight, based on the weight of compoundemployed in the process according to the invention.

Optionally, water can also be added in quantities of 0% to 20% by eight,preferably 0% to 10% by weight.

The compositions consist either of silicon resins which are mixed withfunctional silanes and hydrolysed in organic solvents or of organic(co)polymers which are copolymerized with functional silanes.

The invention further relates to a process for the preparation of acomposition using

(1) polymer components selected from the group consisting of

(A1) polyorganosiloxanes comprising units (T units) of the formula(R₁Si—O_(3/2)) and optionally, units (M units) of the formula(R³Si—O_(1/2))

(A2) polyorganosiloxanes comprising units (Q units) of the formula(Si—O_(4/2)) and, optionally, units (M units) of the formula(R³Si—O_(1/2))

 in which

R is identical or different and represents unhalogenated or halogenatedhydrocarbon radicals having 1 to 18 carbon atom(s) per radical or OR¹,where

R¹ is identical or different and represents hydrogen or a monovalent,unsubstitued or substituted hydrocarbon radical having 1 to 8 carbonatom(s),

 with the proviso that there are from 0.01% to 3.0% by weight ofSi-bonded radicals OR¹

(B) vinyl chloride-hydroxypropyl acrylate copolymers,

(C) vinyl acetate-ethylene copolymer,

(D) polyvinyl chloride,

(E) polyamide,

(F) polyester,

(G) acrylate-polyester copolymers,

(H) polyamide-polyester copolymers,

(I) vinyl acetate-polyester copolymers, and

(J) Monomeric (meth)acrylates, with the proviso that they arecopolymerized with Si-bonded (meth)acrylate group-containing silanes,

(2) a silane of the formula R³ _(x)Si(OR²)_(4−x),

 where

R² is a monovalent, unsubstituted or substituted hydrocarbon radical,

R³ is a monovalent organic radical,

x represents 0 or 1,

(3) optionally, solvent,

4) optionally, catalyst and

5) optionally, water.

Examples of R, R¹, R² and R³ are the examples mentioned above.

The preparation of the compositions according to the invention can takeplace in stirring and mixing units as are conventional in the chemicalindustry. The units should be capable of being set at temperatures inthe range from −10° C. to +150° C. and should be adjustable in theirtemperature. Owing to the use of organic solvents, protection againstexplosion is essential.

Compositions are prepared by simple, thorough mixing of the individualcomponents at temperatures which correspond to the ambient roomtemperature. It is also possible, however, to carry out reactions suchas polymerization, condensation or reaction at reactive groups. Thisrequires thermal monitoring of the reaction events. Such processes arecarried out between 0° C. and 150° C. Preferred temperatures are between10° C. and 120° C. For the sake of simplicity the compositions areprepared at normal atmospheric pressure. The preparation can also takeplace, however, at over pressure up to 20 bar or in vacuum down to 20mbar.

The invention additionally relates to a shaped article or elastomerwhich is coated with a composition according to the invention.

The compositions according to the invention are used as protectivecoatings for elastomeric shaped articles or as topcoats for films, metalparts, woven fabrics, knitted fabrics, nonwovens of synthetic fibresnatural fibres or mineral fibres, which are coated with elastomericmaterials. Examples thereof are injection molded or extruded articles ofelastomeric materials, such as natural rubber, nitrile rubber, butylrubber or silicone rubber. Textile substrates coated with elastomericmaterials, such as conveyor belts, compensators, protective clothing,electrical insulating tubes, electric insulating mats, coated textileswhich can be used for textile structures, for example tents, covers,tarpaulins, exhibit, after treatment according to the invention with thetopcoats according to the invention, mar-resistant, dirt-repellentsurfaces having a reduced coefficient of friction with respect tothemselves and to other materials. As base material, dimethylsiliconerubber is preferably used and not phenylmethylsilicone rubber.

The invention additionally relates to a method of coating shapedarticles or elastomers with the composition according to the invention.

The compositions can be applied by spraying, brushing, knife-coating,with rollers, by tampon printing, by screen printing, dipping, orsimilar techniques. They enter into a firm bond with customary siliconerubber surfaces. Full curing takes place by evaporation of the solventfollowed by poly-condensation. The curing process can be thermallyaccelerated.

The surfaces treated with the topcoats according to the invention aredirt-repellent, mar-resistant and have reduced coefficients of frictionwith respect to themselves and to other materials, such as glass, metal,plastics, fabrics, etc.

It is usual to treat surfaces of silicone rubber mouldings, injectionmouldings, insulating tubes, medical articles, silicone rubber-coatedwoven materials, non-wovens, felts, films or papers with the topcoatsaccording to the invention.

Important properties of the base material, such as tensile strength,extension, elasticity, tear propagation resistance, resistance to heatand cold, to chemicals or light, are not affected by the surfacetreatment.

Advantages of the composition according to the invention are that thecompositions can also be applied to silicone rubber moldings, injectionmoldings, insulating tubes, etc. Application is therefore not limited tocoated fabrics alone. The compositions according to the inventionconsist not only of pure silicone resins but also of copolymers andsilicone components. This makes it possible to obtain a plurality ofproperties, such as dirt repellence, mar resistance and reducedfrictional resistance, with only one topcoat. The topcoats do not causestiffening of the base materials, as is the case with the known methods.This is a significant advantage in particular in the area of coatedtextiles.

The topcoat can be applied in only one operation. Together with the basecoating operation, therefore, only two operations are necessary. In thecase of coated woven fabrics, knitted fabrics or felts it is possible touse customary commercial liquid silicone rubbers as basecoat. Processesare known which, through the addition of adhesion promoters, make itpossible to obtain sufficient adhesion in this operation without aprimer.

EXAMPLE 1

700 kg of a silicone resin solution K Toluol (commercial product ofWacker-Chemie GmbH) and 200 kg of silicone resin solution K 0118(commercial product of Wacker-Chemie GmbH) are placed in a stirrer withdistillation attachment and thoroughly mixed. With continual stiring,324 kg of toluene are distilled off by heating at atmospheric pressure.

The unit and its contents are cooled to room temperature, and 108 kg ofmethyltriethoxysilane (trade name M1-Triethoxysilan from Wacker-ChemieGmbH), 54 kg of tetraethoxysilane (trade name TES 28 from Wacker-ChemieGmbH), 54 kg of vinyltriethoxysilane (trade name Silan GF 56 fromWacker-Chemie GmbH) and 5 kg of zirconium butylate in that order areadded with stiring.

The mixture is stirred at room temperature for 1 hour and then 900 kg ofacetone and 44 kg of water are added with stirring. After stirring atroom temperature for an additional 2 hours, the product is dispensedinto appropriate drums. The clear, colorless liquid has a viscosity ofabout 1.5 mPa·s and a solids content of about 28%.

EXAMPLE 1a

A polyester fabric which has been coated with Elastosil LR 6250 F(commercial product of Wacker-Chemie GmbH) is coated with the solutionfrom Example 1 using a doctor knife, the solvent is evaporated off atroom temperature in 5 min., then the fabric is dried at 150° C. for 5min. The coating weight of the topcoat is about 40 g/m²

EXAMPLE 1b

In a soiling test with carbon black, the fabric provided with thetopcoat according to la shows a markedly reduced uptake of dirt. When anabsorbent paper soiled with carbon black is drawn over the coatingfabric and the uptake of dirt is determined gravimetrically, the uptakeof dirt is found to be reduced by a factor of 8.

1 g of carbon black per m² are applied to an absorbent paper. Thiscarbon black-soiled paper is drawn over the shaped article which is tobe tested for its uptake of dirt. The dirt uptake of the shaped articleis determined gravimetrically. A fabric prepared as described in 1ashows a dirt uptake of 0.02 g/m². The comparison value without topcoatis 0.16 g/m².

EXAMPLE 1c

The fabric coated with Elastosil LR 6250 F is placed coating on coating.A coefficient of friction of 1.4 is measured. The modified fabric fromExample la shows a coefficient of friction of 0.6 in the same test. Thecoefficient of friction of the polyester fabric coated with Elastosil LR6250 F against the uncoated reverse side of the fabric is 0.9. Thelaminate modified according to Example la has a coefficient of frictionof 0.55. The coefficient of friction against stainless steel is 0.8without a topcoat and 0.58 with topcoat.

The coefficients of friction against glass are 1.3 without and 0.7 withtopcoat. Coating as described in Example 1a.

EXAMPLE 2

94 kg of methyl methacrylate, 94 kg of butyl methacrylate and 313 kg oftoluene are placed in a stirrer unit which is fitted with a distillationfacility, which is suitable for separating azeotropically dischargedwater. BY heating the mixture to 105° C., water present is removedazeotropically. When water is no longer discharged from the mixture, thelatter is cooled to 30° C., and 21 kg of Silan GF 31 (commercial productof Wacker-Chemie GmbH) and 2.1 kg of tert-butyl per-ethyl hexanoate areadded. The reaction mixture is heated at reflux, a marked reactioncommending at about 100° C. The mixture is held at reflux for 8 hoursand cooled to 30° C. 15.8 kg of n-butanol and 10.5 kg of SilanM1-Trimethoxy (commercial product of Wacker-Chemie GmbH) are mixed inwith stirring. After stirring for 30 minutes, 720 kg of isopropanol and180 kg of benzine having a boiling range of 120° C. to 140° C. areadded. Stirring is continued for 30 min, The mixture is discharged overa filter.

A clear, colorless solution is obtained with a viscosity of 8 mPa·s anda solids content of 14% by weight.

EXAMPLE 2a

A polyester fabric which has been coated with Elastosil LR 6250 F(commercial product of Wacker-Chemie GmbH) is coated using a brush withthe solution from Example 2; the solvent is evaporated off at roomtemperature in 5 min. and the fabric is then dried at 150° C. for 5 min.The coating weight of the topcoat is about 70 g/m².

EXAMPLE 2b

In a soiling test with carbon black, the fabric provided according to 2awith the topcoat exhibits a markedly reduced uptake of dirt. If a carbonblack-soiled, absorbent paper is drawn over the coated fabric and theuptake of dirt is determined gravimetrically, the uptake of dirt isfound to be reduced by a factor of 6.

The uptake of dirt is carried out as described in Example 1b. Up-take ofdirt without topcoat is 0.19 g/m². Uptake of dirt with topcoat fromExample 2 is 0.03 g/m².

EXAMPLE 2c

On the fabric coated with Elastosil LR 6250 F, coating is placed oncoating. A coefficient of friction of 1.4 is measured. The modifiedfabric from Example 2a shows a coefficient of friction of 0.8 in thesame test. The coefficient of friction of the polyester fabric coatedwith Elastosil LR 6250 F against the uncoated reverse side of the fabricis 0.9. The laminate modified according to Example 2a has a coefficientof friction of 0.65.

The coefficients of friction against stainless steel are 0.8 without and0.52 with topcoat.

The coefficients of friction against glass are 1.3 without and 0.77 withtopcoat. Coating as described in Example 2a.

EXAMPLE 3

47.8 kg of benzine (boiling range 140° C. to 150° C.), 102.6 kg ofmethyl ethyl ketone, 236.2 kg of xylene, 9.9 kg of n-butanol and 60 kgof tetrahydrofuran are placed in a unit fitted with a dissolver disc,and 52 kg of Vinnol E 15/40 A (commercial product of Wacker-Chemie GmbH)are dissolved in this solvent mixture with vigorous mixing. 0.5 kg ofisocyanopropyltriethoxysilane are added and the mixture is boiled atreflux (about 64° C.) for one hour. The mixture is cooled to 30° C., and50 kg of tetrahydrofuran, 350 kg of toluene and 1000 kg of acetone areadded. Intensive mixing is carried out for 30 minutes. The clear,colorless product has a viscosity of 11 mPa·s and a solids content ofabout 2.8% by weight.

EXAMPLE 3a

A polyester fabric which has been coated with Elastosil LR 6250 F(commercial product of Wacker-Chemie GmbH) is dipped in the solutionfrom Example 3. After removal from the dipping bath, the solvent isevaporated off at room temperature in 5 min. and the fabric is thendried at 150° C. for 5 min. The coating weight of the top coat is about20 g/m².

EXAMPLE 3b

In a soiling test with carbon black, the fabric provided according to 3awith the topcoat shows a markedly reduced uptake of dirt. If a carbonblack-soiled, absorbent paper is drawn over the coated fabric and theuptake of dirt is determined gravimetrically, then the uptake of dirt isfound to be reduced by a factor of 9.

Uptake of dirt is carried out as described in Example 1b. Uptake of dirtwithout topcoat is 0.17 g/m². Uptake of dirt with topcoat from Example 3is 0.019 g/m².

EXAMPLE 3c

On the fabric coated with Elastosil LR 6250 F, coating is placed oncoating. A coefficient of friction of 1.4 is measured. The modifiedfabric from Example 3a shows a coefficient of friction of 0.7 in thesame test. The coefficient of friction of the polyester fabric coatedwith Elastosil LR 6250 F against the uncoated reverse side of the fabricis 0.9. The laminate modified according to Example 3 a has a coefficientof friction of 0.48. The coefficients of friction against stainlesssteel are 0.8 without and 0.62 with topcoat.

The coefficients of friction against glass are 1.3 without and 0.52 withtopcoat. Coating as described in Example 3a.

Soiling Test

An absorbent crepe paper is loaded with 1 g of carbon black per m² andis applied with cyclical movements to the fabric coated in accordancewith the invention and a comparison fabric. In general, the fabriccoated in accordance with the invention took up from 0.01 g/m² to 0.05g/m² of carbon black, while the comparison fabric coated not inaccordance with the invention took up from 0.1 g/m² to 0.3 g/m².

Determination of the Coefficient of Friction

The coefficient of friction is determined in accordance with ASTMStandard D-1894 with a slip/peel tester model SP-103 from the companyInstrumentos Inc., Cleveland, Ohio.

What is claimed is:
 1. A coating composition liquid at room temperature,said coating composition containing one or more liquid soil-reducingand/or friction-reducing compositions consisting of silicon resins andoptionally one or more organic (co)polymers in admixture with functionalsilanes, said admixture hydrolyzed in organic solvents, saidsoil-reducing and/or friction-reducing compositions consisting of, (1) apolymer component selected from the group consisting of (A) a siliconresin mixture of (A1) polyorganosiloxanes comprising units (T units) ofthe formula (R₁Si—O_(3/2)) and optionally, units (M units) of theformula (R₃Si—O_(1/2)), and (A2) polyorganosiloxanes comprising units (Qunits) of the formula (Si—O_(4/2)) and, optionally, units (M units) ofthe formula (R₃Si—O_(1/2)),  wherein R is identical or different and isa non-halogenated aliphatic hydrocarbon radical having 1 to 18 carbonatom(s) per radical or a halogenated hydrocarbon radical selected fromthe group consisting of the 3,3,3-trifluoro-n-propyl radical, the2,2,2,2′,2′,2′-hexafluoroisopropyl radical, and the heptafluoroisopropyl radical, or OR¹, where R¹ is identical or different andrepresents hydrogen or a monovalent, unsubstituted or substitutedhydrocarbon radical having 1 to 8 carbon atom(s), with the proviso thatA1 and A2 contain from 0.01% to 3.0% by weight, of Si-bonded radicalsOR¹,  and optionally one or more organic (co)polymer of (B) through (J)(B) vinyl chloride-hydroxypropyl acrylate copolymers, (C) vinylacetate-ethylene copolymer, (D) polyvinyl chloride, (E) polyamide, (F)polyester, (G) acrylate-polyester copolymers, (H) polyamide-polyestercopolymers, (I) vinyl acetate-polyester copolymer, and (J) monomeric(meth)acrylates, with the proviso that they are copolymerized withSi-bonded (meth)acrylate group-containing silanes,  with (2) a silane ofthe formula R³ _(x)Si(OR²)_(4-x),  where R² is a monovalent,unsubstituted or substituted hydrocarbon radical, R³ is a monovalent,substituted or unsubstituted alkyl, alkenyl, or cycloalkyl radical, xrepresents 0 or 1,  and containing (3) from about 10% to about 90% byweight based on the total weight of the composition of one or moreorganic solvents, (4) optionally, one or more catalysts, and (5)optionally, water.
 2. Composition according to claim 1, characterized inthat the polyorganosiloxanes (A1) the ratio of M units to T units is0.1:1 to 1.2:1 and in the polyorganosiloxanes (A2) the ratio of M unitsto Q units is 0.01:1 to 2.1:1.
 3. The composition of claim 1 whereinsaid polymer component is selected from the group consisting of: (A1)polyorganosiloxanes comprising units (T units) of the formula(R₁Si—O_(3/2)) and optionally, units (M units) of the formula(R₃Si—O_(1/2)) (A2) polyorganosiloxanes comprising units (Q units) ofthe formula (Si—O,_(4/2)) and, optionally, units (M units) of theformula (R₃Si—O_(1/2)),  and mixtures thereof;  in which R is identicalor different and represents alkyl radicals having 1 to 18 carbon atom(s)per radical or OR¹, where R¹ is identical or different and representshydrogen or a monovalent, unsubstituted or substituted hydrocarbonradicals having 1 to 8 carbon atom(s),  with the proviso that there arefrom 0.01% to 3.0% by weight of Si-bonded radicals OR¹; and  optionallyone or more of (B) through (I): (B) vinyl chloride-hydroxypropylacrylate copolymers, (C) vinyl acetate-ethylene copolymer, (D) polyvinylchloride, (E) polyamide, (F) polyester, (G) acrylate-polyestercopolymers, (H) polyamide-polyester copolymers, and (I) vinylacetate-polyester copolymers.
 4. The composition of claim 3 wherein R¹is a monovalent hydrocarbon radical having 1 to 8 carbon atoms.
 5. Thecomposition of claim 3 where in the polyorganosiloxanes (A1) the ratioof M units to T units is 0.1:1 to 1.2:1, and in the polyorganosiloxanes(A2) the ratio of M units to Q units is 0.01:1 to 2.1:1.
 6. Thecomposition of claim 1, wherein R is identical or different andrepresents non-halogenated hydrocarbon radicals having 1 to 18 carbonatom(s) per radical or OR¹, where R¹ is identical or different andrepresents hydrogen or a monovalent, unsubstituted or substitutedhydrocarbon radical having 1 to 8 carbon atom(s),  with the proviso thatA1 and A2 contain from 0.01 % to 3.0% by weight, of Si-bonded radicalsOR¹, wherein a mixture of (A1) and (A2) is present, and at least one of(B), (C), (G) or (J) is present.
 7. The composition of claim 1, whereinR is identical or different and represents non-halogenated hydrocarbonradicals having 1 to 18 carbon atom(s) per radical or OR¹, where R¹ isidentical or different and represents hydrogen or a monovalent,unsubstituted or substituted hydrocarbon radical having 1 to 8 carbonatom(s),  with the proviso that A1 and A2 contain from 0.01 % to 3.0% byweight, of Si-bonded radicals OR¹, wherein a mixture of (A1) and (A2) ispresent, and (B) is present.
 8. The composition of claim 1, wherein R isidentical or different and represents non-halogenated hydrocarbonradicals having 1 to 18 carbon atom(s) per radical or OR¹, where R¹ isidentical or different and represents hydrogen or a monovalent,unsubstituted or substituted hydrocarbon radical having 1 to 8 carbonatom(s),  with the proviso that A1 and A2 contain from 0.01 % to 3.0% byweight, of Si-bonded radicals OR¹, wherein a mixture of (A1) and (A2) ispresent, and (G) is present.
 9. The composition liquid at roomtemperature of claim 1, consisting of the reaction product of, (1) amixture of (A1) polyorganosiloxanes comprising units (T units) of theformula (R₁Si—O_(3/2)) and optionally, units (M units) of the formula(R₃Si—O_(1/2)), (A2) polyorganosiloxanes comprising units (Q units) ofthe formula (Si—O_(4/2)) and, optionally, units (M units) of the formula(R₃Si—O_(1/2)),  wherein R is identical or different and representsnon-halogenated hydrocarbon radicals having 1 to 18 carbon atom(s) perradical or OR¹, where R¹ is identical or different and representshydrogen or a monovalent, unsubstituted or substituted hydrocarbonradical having 1 to 8 carbon atom(s),  with the proviso that A1 and A2contain from 0.01% to 3.0% by weight, of Si-bonded radicals OR¹, and  atleast one of (B) through (J): (B) vinyl chloride-hydroxypropyl acrylatecopolymers, (C) vinyl acetate-ethylene copolymer, (D) polyvinylchloride, (E) polyamide, (F) polyester, (G) acrylate-polyestercopolymers, (H) polyamide-polyester copolymers, (I) vinylacetate-polyester copolymer, and (J) monomeric (meth)acrylates, with theproviso that they are copolymerized with Si-bonded (meth)acrylategroup-containing silanes, (2) a silane of the formula R³_(x)Si(OR²)_(4-x),  where R² is a monovalent, unsubstituted orsubstituted hydrocarbon radical, R³ is a monovalent organic radical, xrepresents 0 or 1; (3) from about 10% to 90% by weight based on thetotal weight of the composition of one or more organic solvents, (4)optionally, a catalyst and (5) optionally, water.
 10. A process for thepreparation of a coating composition of claim 1, wherein (1) a mixtureof (A1) polyorganosiloxanes comprising units (T units) of the formula(R₁Si—O_(3/2)) and optionally, units (M units) of the formula(R₃Si—O_(1/2)), (A2) polyorganosiloxanes comprising units (Q units) ofthe formula (Si—O_(4/2)) and, optionally, units (M units) of the formula(R₃Si—O_(1/2)),  in which R is identical or different and representunhalogenated or halogenated hydrocarbon radicals having 1 to 18 carbonatom(s) per radical or OR¹, where R¹ is identical or different andrepresents hydrogen or a monovalent, unsubstituted or substitutedhydrocarbon radical having 1 to 8 carbon atom(s),  with the proviso thatthere are from 0.01% to 3.0% by weight of Si-bonded radicals OR¹, (B)vinyl chloride-hydroxypropyl acrylate copolymers, (C) vinylacetate-ethylene copolymer, (D) polyvinyl chloride, (E) polyamide, (F)polyester, (G) acrylate-polyester copolymers, (H) polyamide-polyestercopolymers, (I) vinyl acetate-polyester copolymer, and (J) monomeric(meth)acrylates, with the proviso that they are copolymerized withSi-bonded (meth)acrylate group-containing silanes,  are reacted with (2)a silane of the formula R³ _(x)Si(OR²)_(4-x),  where R² is a monovalent,unsubstituted or substituted hydrocarbon radical, R³ is a monovalentorganic radical, x represents 0 or 1, wherein one or more solvents,catalysts, and/or water are optionally added prior to, during, and/orsubsequent to the step of reacting.
 11. A process for the preparation ofa coating composition of claim 1 which is liquid at room temperature,comprising mixing, (1) a polymer component comprising (A1)polyorganosiloxanes consisting of units (T units) of the formula(R₁Si—O_(3/2)) and optionally, units (M units) of the formula(R₃Si—O_(1/2)), and (A2) polyorganosiloxanes comprising units (Q units)of the formula (Si—O_(4/2)) and, optionally, units (M units) of theformula (R₃Si—O_(1/2)),  wherein R is identical or different andrepresents optionally halogenated hydrocarbon radicals having 1 to 18carbon atom(s) per radical or OR¹, where R¹ is identical or differentand represents hydrogen or a monovalent, unsubstituted or substitutedhydrocarbon radical having 1 to 8 carbon atom(s),  with the proviso thatA1 and A2 contain from 0.01% to 3.0% by weight, of Si-bonded radicalsOR¹,  with (2) a silane of the formula R³ _(x)Si(OR²)_(4-x,)  where R²is a monovalent, optionally substituted hydrocarbon radical, R³ is amonovalent, substituted or unsubstituted alkyl, alkenyl, or cycloalkylradical, x represents 0 or 1,  and hydrolyzing the mixture with water inthe presence of an organic solvent and optionally a catalyst.
 12. Thecomposition of claim 1, wherein the weight ratio of polymer (1) tosilane (2) is from 100:2 to 100:20.
 13. A shaped article or elastomerwherein the shaped article or elastomer has been coated with a coatingcomposition which is liquid at room temperature, said coatingcomposition containing one or more soil-reducing and/orfriction-reducing compositions consisting of silicon resins, inadmixture with functional silanes, said admixture hydrolyzed in organicsolvents, and optionally one or more organic (co)polymers saidsoil-reducing and/or friction-reducing compositions consisting of (1) apolymer component selected from the group consisting of (A) a siliconresin mixture of (A1) polyorganosiloxanes consisting of units (T units)of the formula (R₁Si—O_(3/2)) and optionally, units (M units) of theformula (R₃Si—O_(1/2)), and (A2) polyorganosiloxanes comprising units (Qunits) of the formula (Si—O_(4/2)) and, optionally, units (M units) ofthe formula (R₃Si—O_(1/2)),  wherein R is identical or different and isa non-halogenated hydrocarbon radical having 1 to 18 carbon atom(s) perradical or a halogenated hydrocarbon radical selected from the groupconsisting of the 3,3,3-trifluoro-n-propyl radical, the2,2,2,2′,2′,2′-hexafluoroisopropyl radical, and the heptafluoroisopropyl radical, or OR¹, where R¹ is identical or different andrepresents hydrogen or a monovalent, unsubstituted or substitutedhydrocarbon radical having 1 to 8 carbon atom(s),  with the proviso thatA1 and A2 contain from 0.01% to 3.0% by weight, of Si-bonded radicalsOR¹, and optionally one or more organic (co)polymer of (B) through (J):(B) vinyl chloride-hydroxypropyl acrylate copolymers, (C) vinylacetate-ethylene copolymer, (D) polyvinyl chloride, (E) polyamide, (F)polyester, (G) acrylate-polyester copolymers, (H) polyamide-polyestercopolymers, (I) vinyl acetate-polyester copolymer, and (J) monomeric(meth)acrylates, with the proviso that they are copolymerized withSi-bonded (meth)acrylate group-containing silanes,  with (2) a silane ofthe formula R³ _(x)Si(OR²)_(4-x),  where R² is a monovalent, optionallysubstituted hydrocarbon radical, R³ is a monovalent, substituted orunsubstituted alkyl, alkenyl, or cycloalkyl radical, x represents 0 or1,  and containing (3) from about 10% to about 90% by weight based onthe total weight of the composition of one or more organic solvents, (4)optionally, one or more catalysts, and (5) optionally, water.
 14. Theshaped article or elastomer of claim 13 where in the polyorganosiloxanes(A1) the ratio of M units to T units is 0.1:1 to 1.2:1, and in thepolyorganosiloxanes (A2) the ratio of M units to Q units is 0.01:1 to2.7:1.
 15. A method of increasing the resistance to soiling and loweringthe coefficient of friction of a shaped article or elastomer, saidmethod comprising coating the shaped article or elastomer with acomposition liquid at room temperature, said coating compositioncontaining one or more soil-reducing and/or friction-reducingcompositions consisting of silicon resins,in admixture with functionalsilanes, said admixture hydrolyzed in organic solvents, and optionallyone or more organic (co)polymers said soil-reducing and/orfriction-reducing compositions consisting of (1) a polymer componentselected from the group consisting of (A) a silicon resin mixture of(A1) polyorganosilicon resins consisting of units (T units) of theformula (R₁Si—O_(3/2)) and optionally, units (M units) of the formula(R₃Si—O_(1/2)), and (A2) polyorganosilicon resins consisting of units (Qunits) of the formula (Si—O_(4/2)) and, optionally, units (M units) ofthe formula (R₃Si—O_(1/2)),  wherein R is identical or different and isa non-halogenated aliphatic hydrocarbon radical having 1 to 18 carbonatom(s) per radical or a halogenated hydrocarbon radical selected fromthe group consisting of 3,3,3-trifluoro-n-propyl radical, the2,2,2,2′,2′,2′-hexafluoroisopropyl radical, and the heptafluoroisopropyl radical, or OR¹, where R¹ is identical or different andrepresents hydrogen or a monovalent, unsubstituted or substitutedhydrocarbon radical having 1 to 8 carbon atom(s),  with the proviso thatA1 and A2 contain from 0.01 % to 3.0 % by weight, of Si-bonded radicalsOR¹, and  optionally one or more organic (co)polymer of (B) through (J):(B) vinyl chloride-hydroxypropyl acrylate copolymers, (C) vinylacetate-ethylene copolymer, (D) polyvinyl chloride, (E) polyamide, (F)polyester, (G) acrylate-polyester copolymers, (H) polyamide-polyestercopolymers, (I) vinyl acetate-polyester copolymer, and (J) monomeric(meth)acrylates, with the proviso that they are copolymerized withSi-bonded (meth)acrylate group-containing silanes,  with (2) a silane ofthe formula R³ _(x)Si(OR²)_(4-x),  where R² is a monovalent, optionallysubstituted hydrocarbon radical, R³ is a monovalent, substituted orunsubstituted alkyl, alkenyl, or cycloalkyl radical, x represents 0 or1,  and containing (3) from about 10% to about 90% by weight based onthe total weight of the composition of one or more organic solvents, (4)optionally, one or more catalysts, (5) optionally, water, and  allowingsaid liquid coating to cure to a solid coating.
 16. The method of claim14 wherein at least one of (B) through (J) is present.
 17. A process forthe preparation of a soil and/or friction reducing coating compositionliquid at room temperature prior to cure, comprising mixing, (1) apolymer component selected from the group consisting of (A) a mixture of(A1) polyorganosiloxanes consisting of units (T units) of the formula(R₁Si—O_(3/2)) and units (M units) of the formula (R₃Si—O_(1/2)), (A2)polyorganosiloxanes comprising units (Q units) of the formula(Si—O_(4/2)) and units (M units) of the formula (R₃Si—O_(1/2)),  whereinR is identical or different and represents optionally halogenatedhydrocarbon radicals having 1 to 18 carbon atom(s) per radical or OR¹,where R¹ is identical or different and represents hydrogen or amonovalent, unsubstituted or substituted hydrocarbon radical having 1 to8 carbon atom(s),  with the proviso that A1 and A2 contain from 0.01 %to 3.0% by weight, of Si-bonded radicals OR¹,  with (2) a silane of theformula R³ _(x)Si(OR²)_(4-x),  where R² is a monovalent, optionallysubstituted hydrocarbon radical, R³ is a monovalent, substituted orunsubstituted alkyl, alkenyl, or cycloalkyl radical, x represents 0 or1,  and hydrolyzing the mixture with water in the presence of an organicsolvent and optionally a catalyst.
 18. The method of claim 17, where inthe organopolysiloxanes (A1) the ratio of M units to T units is 0.1:1 to1.2:1, and in the polyorganosiloxanes (A2) the ratio of M units to Qunits is 0.01:1 to 2.7:1.
 19. The coating composition of claim 16wherein said silicon resins (A1) and (A2) are solids.
 20. The coatingcomposition of claim 17 wherein said silicon resins (A1) and (A2) aresolids.
 21. The coating composition of claim 18 wherein said siliconresins (A1) and (A2) are solids.
 22. A coating composition liquid atroom temperature, said coating composition containing one or more liquidsoil-reducing and/or friction-reducing compositions consisting ofsilicon resins and at least one organic (co)polymer in admixture withfunctional silanes, said admixture hydrolyzed in organic solvents, saidsoil-reducing and/or friction-reducing compositions consisting of, (1) apolymer component comprising a mixture of (A) polyorganosiloxanescomprising units (Q units) of the formula (Si—O_(4/2)) and, optionally,units (M units) of the formula (R₃-O_(1/2),)  wherein R is identical ordifferent and is a non-halogenated aliphatic hydrocarbon radical having1 to 18 carbon atom(s) per radical or a halogenated hydrocarbon radicalselected from the group consisting of the 3,3,3-trifluoro-n-propylradical, the 2,2,2,2′,2′,2′-hexafluoroisopropyl radical, and theheptafluoro isopropyl radical, or OR¹, where R¹ is identical ordifferent and represents hydrogen or a monovalent, unsubstituted orsubstituted hydrocarbon radical having 1 to 8 carbon atom(s),  with theproviso that (A) contains from 0.01 % to 3.0% by weight, of Si-bondedradicals OR¹, at least one organic (co)polymer of (B) through (J) (B)vinyl chloride-hydroxypropyl acrylate copolymers, (C) vinylacetate-ethylene copolymer, (D) polyvinyl chloride, (E) polyamide, (F)polyester, (G) acrylate-polyester copolymers, (H) polyamide-polyestercopolymers, (I) vinyl acetate-polyester copolymer, and (J) monomeric(meth)acrylates, with the proviso that they are copolymerized withSi-bonded (meth)acrylate group-containing silanes,  with (2) a silane ofthe formula R³ _(x)Si(OR²)_(4-x),  where R² is a monovalent,unsubstituted or substituted hydrocarbon radical, R³ is a monovalent,substituted or unsubstituted alkyl, alkenyl, or cycloalkyl radical, xrepresents 0 or 1,  and containing (3) from about 10% to about 90% byweight based on the total weight of the composition of one or moreorganic solvents, (4) optionally, one or more catalysts, and (5)optionally, water.
 23. The composition of claim 22 wherein (B) ispresent.
 24. The composition of claim 22 wherein (G) is present.
 25. Thecomposition of claim 22 wherein (J) is present.